Colored condensation products and process of making same.



UNITED sTATEs PATENT ossiciiz- GADIE'ST ENGI, O13 BASEL, SWITZERLAND, AQSIGNQE T SOCIETY 03? CHE'MZOAL INDUSTHIY IN BASLE, OF BASEL, 3'WI1ZERLAND.

COLORED OONDENSATIQN PRODUCTS AND PROCESS OF MAKING: SAME.

1% Drawing.

Specification of Letters Yateut.

Application filed May 21, 1912.

Patented Nov 5, 1912.

Serial No. 698,776.

Switzerland, have invented new Colored- Condensation lh'oducts and Processes of Malzlug: Some, of which the following a lull, .nd exact specification. I

l hm found. that new, intense red, blue led and violet colored condensation products obtained by the action 03". halide of r v natty acids of the formula for instance the chlorid of phenylocetic acid, on an indigo substance, as for instance indigo and its derivatives.

The invention is illustrated by the fol- I lowing exmuples, the parts being by Weight:

hslf an hour, the mass is allowed to cool;

diluted with 250300 parts of nitrobenzene c1- of xylene, again heated for a short time to boiling and sepamted by filtration from the eventually not dissolved parts. By cooling down the filtered liquid, the new condensation product separates in form of yellow fluorescence.

lowing formulae:

bright red small crystals which are filtered, Washed with alcohol. and dried. The con densati'on product thus obtained is con1- pletely insoluble in water, dilute sllmlis and dilute acids. In organic solvents, as Xylene, toluene, nitrobenzene it is dillicultly soluble when cold, but easily soluble when hot with u Carmine red coloration and an intense Concentrated sulfuricocid dissolves it to av yellow orange solulion of yellowish fluorescence. solution in sulfuric acid with ice-waiter the unaltered condensationproduct separates in form of cormine red flakes. In fuming sulfuric acid of 2d per cent. anhydrid the product dissolves with an intense orange color, and on heating the so obtained solution. sullon atiou incurs, as no further precipitation takes place when the solution is poured into water m1 us from the thus obtained dilute solution the formed sulfuric acid can be salted out by an sdditiou olicommou salt. This sul'lcnic acid dyes Wool and sill; in on acid bath carmine red tints. lie-Mine the condensation product at a high temp ut-uic it is suhliumted and gives cormine red vapors.

An elementary analysis shows that the formation of the new condcnsotion product occurs by the reaction of 2 l'nolecules of chlorid of phenylacetic acid on. l. molecule of indigmwhile hydrochloric acid and Water are split oil, probablyaccording to the fol- Calculated for C H N G Found-- l c=s3.11%. 82.79% H: 3.90% 4.29% N: cocoa, 5.95% 0:. 6.93%

benzene ind 12 pacts of ohlorid phenyL acetic acid, on an oil bath, 01-1 to 1% hours, l and the reaction mass assumes a. red colors- On cooling the condensation product separates in form of small red crystals.

Example III: parts of 7.Y-dimethyllindigo are heated to other with lo parts of chlorid of phenylacetic acid on an. oil bath, for 20 to 30 minutes to C. (temperature of the oil bath) in s vessel provided with a reflux condenser, whereby an evolution of hydrochloric acid takes place By diluting its in a. vessel. provided with a reflux condenser. l tion. The massis then cooled down and 9c about li'O parts of nitrobenzene are added. thereto and the mixture again shortly heated to'boiling, filtered and cooled down. The separated, vivid red colored crystals are filtered, washed successively with nitrobenzone and alcohol and dried. The product thus obtained dissolves in nitrobenzene to a carmine redsolution of yellow fluorescence.

Example IV: 3 parts of 5.5-dibrom.indigo are heated to boiling with 12 parts of chlorid of phenyl-acetic acid, whereby the mass of reaction becomes deep red. After the heating has been. continued for about 1 hour, the

mass is diluted with 3Q parts of nitrobenzene and worked up as in the foregoing examples. The brominated condensation product thus obtained constitutes blue red crystals analogous to the condensation product de .rived from indigo. Its carrnine red solution in organic solvents'shows also the intense yellow fluorescence, which is characteristic for the bodies of this group.

Example V: 3 parts of tetrabroinindigo are boiledior some time with 10 to 1,2 parts of chlorid of phenylacetic acid and'tlie reaction mass worked up in the above specified -1nann'er, whereby the condensation product is at first obtained in the form of gra crystalline "powder assuming by grinding a blue red color. By pouring its orange yellow sulfuric solution into icewvatcr, the unaltered condensation product separates as intensive blue red colored flakes. In organic solvents, as for instance Xylene, it

dissolves to a 'carn'iinered solution of yellow uorescence.

In a similar manner is ef fected the preparation of condensation prod note when other substitution products of indigo, as for instance hexabromindigo, 7.7- dimethoxyindigo, 5.5-dimethoxyindigo, tetramethylindigo, indigo, 5.7- 5.7-tetrachlorindigo, 4.5 43.5- tetrachlorindigo, Inonobromindigo, monochlorindigo, are employed or when the chlo-' rid of phenylacetic acid is replaced by its homologues, acts.

The products obtained according to the analogous or substitution prodhot xylene or hot I carinine color and cence and dissolving 1n goncentrated sulhexamethylindigo, dichlordescribed process and their sulfonic acids are to be employed in the industry of dyestuds.

What I claim is: I

, 1. The described process for the manufac ture of new colored condensation products consisting in treating an indigo substance with a halid of an arylated fatty acid, substantially as described.

2. The described processfor the manufacture of new colored condensation products consisting in with a halid of phenylacetic acid, substantially as described.

3.. As new products the condensation products derived from an indigo substance and a halid of an arylated fatty acid, forming in dry state red to violet powders, insoluble in water, diflicultly soluble in cold xylene and nitrobcnzene, but easily soluble in these solvents when hot with a carinine color, the so 'lutions showing an intense yellow fluorescence, and dissolving in concentrated sulfuric' acid with yellowish orange to orange vcolor, from which solutions on'addition of ice-water the unaltered condensation product is precipitated in the form of bright red to violet flakes. As new products the condensation producis'derived from an indigo substance and a halid of phenyl-acetic acid, forming in dry state red to violet powders, insoluble in water, ditficultly soluble in cold, but easily soluble in hot Xylene and nitrobenzene with intensive yellow fluore's furic acid with yellowish orange to orange color, from which solutions on addition of 1ce-water the unaltered condensation product is precipitated in the to violet flakes. In witness whereof Ihave hereunto signed my name this 9th day of May1912, in the presence of'two subscribing Witnesses.

GADIENT ENGI.

Witnesses AMAND RITTER, Gno. Girrono.

form of bright red 

